Herbicidal oxime esters of phenoxyalkanoic esters and their use as selective herbicides

ABSTRACT

Oxime esters of phenoxyalkanoic acids, having a common core of the formula   WHEREIN R1 and R2 individually or jointly are hydrocarbyl or substituted hydrocarbyl, R3 is hydrogen or lower alkyl, and the phenyl group carries up to three substituents, are herbicides harmless to cereal crops at application rates at which they destroy or at least severely damage numerous common weeds, including millets, which are intermingled with the crop plants.

United States Patent Niisslein et al.

Dec. 9, 1975 1 HERBXCIDAL OXIME ESTERS OF PHENOXYALKANOIC ESTERS AND THEIR USE AS SELECTIVE HERBICIDES [75] Inventors: Ludwig Ni'isslein; Friedrich Arndt,

both of Berlin, Germany [73] Assignee: Schering AG, Berlin and Bergkamen, Germany [22] Filed: Dec. 12, 1973 [21] Appl, No: 424,005

[52] US. Cl 260/566 AE; 71/121 [51] Int. Cl. C07C 131/00 [58] Field of Search .4 260/566 AB [56] References Cited UNITED STATES PATENTS 3.165.392 l/l965 Koopman .1 260/566 AE 3.169989 2/1965 Tieman et all rrrrrrrrrrrrr 1. 260/566 AE 3,592.920 7/1971 Gutman et al 260/566 AE Primary Examiner-Gerald A. Schwartz Attorney, Agent, or FirmJoseph F. Padlon [57] ABSTRACT Oxi ne esters of phenoxyalkanoic acids, having a common core of the formula wherein R, and R individually or jointly are hydrocarbyl or substituted hydrocarbyl, R is hydrogen or lower alkyl. and the phenyl group carries up to three substituents, are herbicides harmless to cereal crops at application rates at which they destroy or at least severely damage numerous common weeds including millets, which are intermingled with the crop plants.

3 Claims, N0 Drawings HERBICIDAL OXIME ESTERS OF PHENOXYALKANOIC ESTERS AND THEIR USE AS SELECTIVE HERBICIDES This invention relates to herbicides, and particularly to phenoxyalkanoic acid derivatives which are effective herbicides.

The known herbicides are not fully effective in combating millets in cereal crops. Millet is the common name of various small-seeded grasses which are annual, warm-season plants. Some are of value as crop plants in other countries, but they are generally considered weeds in North America, Typical millets which may seriously threaten a cereal crop are Digitaria sanguinalis, Echinochloa crus galli, and Seraria faberii.

The primary object of the invention is the provision of herbicidal agents specifically effective against millets, preferably also effective against other weeds, while harmless to cereal crops when applied to intermingled stands of the crops and weeds in concentrations effective severely to damage the weeds.

Such herbicidal agents have been found in the oxime esters of phenoxyalkanoic acids of the formula wherein R and R are members of the group consisting of hydrogen, aliphatic, cycloaliphatic, araliphatic, and aromatic hydrocarbyl groups, and monoand polysubstitution products of such hydrocarbyl groups, not more than one of R andR being hydrogen, or R and R jointly constitute a divalent hydrocarbyl radical which may be interrupted by oxygen or nitrogen; R is hydrogen or lower alkyl; and X, Y, and Z are members of the group consisting of hydrogen, lower alkyl, lower alkoxy, lower haloalkyl, and halogen.

R and R thus may be aromatic hydrocarbyl, such as phenyl or naphthyl; aliphatic hydrocarbyl having one to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, and the higher homologs thereof; also cycloaliphatic hydrocarbyl having five to eight carbon atoms, such as cyclohexyl; furthermore araliphatic hydrocarbyl such as benzyl orphenylethyl; and substitution products of such hydrocarbyl radicals, the substituents being lower alkyl, such as methyl or ethyl, halogen, such as chlorine or bromine, lower alkoxy, such as methoxy or ethoxy. The lower alkyls which may constitute R may have one to three carbon atoms.

When R and R jointly constitute a divalent hydrocarbyl radical, they may form a cycloaliphatic ring of five to eight carbon atoms with the carbon atom to which they are connected, such as cyclohexylidene, cyclooctylidene, and such rings may be further substituted by lower alkyl, such as methyl, and may also be interrupted by nitrogen or oxygen atoms.

The compounds of the invention have a surprisingly good herbicidal effect against the millets mentioned LII LII

above. Best results are generally obtained by compounds in which R and R are hydrogen, alkyl having up to six carbon atoms, phenyl, nitrophenyl, loweralkoxy-lower-alkyl, or phenoxy-lower-alkyl, not more than one of R and R being hydrogen. Equally effective are compounds in which R and R jointly constitute a divalent aliphatic radical having a chain or four or five carbon atoms and a total of up to eight carbons including those inside chains. Lower alkyl and lower alkoxy include radicals having up to three carbon atoms.

In the preferred compounds of the invention, R is hydrogen or methyl, X is chlorine, bromine or methyl, Y is chlorine, hydrogen, or methyl, and Z is hydrogen or chlorine. Particularly good results are achieved with compounds in which at least one of X, Y, and Z is halogen, and lower alkyl and lower alkoxy are methyl and methoxy respectively.

in addition to the millets mentioned above, the compounds of the invention have strong herbicidal effects on common weeds including Sinapis sp., Solanum sp., Medicago sp., Stellaria media, Senecio vulgaris, Matricuria chamomilla, Lamium amplexicaule, Centaurea cyanm', Amaranthus retroflexus, Galium aparine, Chrysanthemum segetum, lpomea purpurea, Polygonum lapathifolium, and others. When these weeds are intermingled with crop plants such as cereal crops (barley, wheat, oats, rye, corn, rice) and potatoes, the weeds may be damaged severely or destroyed by the compounds of the invention applied at rates at which the crop plants are unaffected. Amounts of 0.5 to 3 kg per hectare are effective in most instances, but higher application rates may be necessary under unusual conditions, and smaller amounts may be adequate under others. i

The compounds of the invention are normally applied in the form of compositions containing 20 to parts of the active ingredients in intimate mixtures with 80 to 20 parts inert matter serving as a carrier, the combined amount of active agents and carrier being parts, all parts being by weight, and the composition preferably containing up to 20 parts of surfactant. The latter may serve as a wetting agent or emulsifier to enhance the herbicidal effect in a known manner although it may not be herbicidal in itself.

The active agents of the invention are compatible with each other and with many other herbicides such as maleic hydrazide, 3-amino-l,2,4-triazole, N-( 1,1- dimethyl-2-propyl)-3,5-dichlorobenzamide, N,N-di-(npropyl)-2,6-dinitro-4-trifluoromethylaniline, 4-amino- 3,5,6-trichloropicolinic acid, 1 ,l '-dimethyl-4,4'- bipyridylium salts, and may be combined with the lastmentioned other herbicides in herbicidal compositions with the expected loss in selectivity where this is tolerable.

The herbicidal compositions in which compounds of the invention constitute active agents are formulated in a manner conventional in this art according to the desired method of application. Solid carriers are used in pulverulent or granular compositions, and aqueous liquids or organic solvents for liquid compositions in which the active agents of the invention may constitute a dispersed, separate phase.

Suitable liquid carriers include water, hydrocarbons including aliphatic petroleum fractions, also benzene, toluene, cyclohexanone, and-isophorone. Solid carriers include silica gel, talcum, attaclay, kaolin and other clays, limestone,but also cereal flour. Suitable surfactants include, but are not limited to, calcium lignosulfonate, polyoxyethylene octylphenol ether, naphthale nesulfonic acid, phenolsulfonic acids, fatty alcohol sulfates, and alkali metal and alkaline earth metal salts of fatty acids.

The compositions may be applied in the usual manner. Aqueous compositions may thus be sprayed at a rate of 100 to l,000 liters per hectare, or even higher when all weeds present are to be destroyed, and other modes of application will readily suggest themselves to suit specific requirements.

The compounds of the invention may be prepared by reacting oximes of the formula or their alkali metal salts, particularly the potassium or sodium salts, with phenoxyalkanoyl halides of the formula Y O CH CO Halogen wherein R,, R R X, Y, and Z are as defined above, in the presence of acid acceptors which may be organic or inorganic bases, triethylamine, dimethylaniline, pyridine, sodium carbonate, and sodium hydroxide being representative of suitable acceptors. The reaction may be performed in an inert organic solvent such as a chlorinated hydrocarbon, ether, ester, nitrile, carboxylic acid amide, or water. Methylene chloride, tetrahydrofuran, dioxane, ethyl acetate, acetonitrile, and dimethylformamide are preferred. Chlorine and bromine are the preferred halogens.

The oximes may also be reacted with anhydrides of the fonnula Y -O-CH-CO-O-CO-CHO- in the optional presence of an acid acceptor, such as pyridine, N,N-dimethylaniline, or triethylamine, and an inert solvent, benzene, pyridine, tetrahydrofuran, dioxane, dimethylsulfoxide, acetonitrile, and dimethylformamide being typical, suitable solvents.

The following Example illustrates the preparation of the compounds of the invention.

EXAMPLE I 29.4 g 2,4-Dichlorophenoxyacetylchloride was added dropwise with stirring to a solution of 14.1 g methyl-( l-methylpropyl)-ketoxime and 12.4 g triethylamine in 200 ml acetonitrile, whereby the temperature of the mixture rose to 45C. The mixture was further stirred for 3 hours, and then poured into 2 liters water. An oily precipitate fonned and was extracted with ethyl ether. The solvent phase was separated, washed sequentially with dilute sodium hydroxide solution and water, and dried over desiccated magnesium sulfate. The solvent was partly evaporated at ambient pressure and ultimately in a high vacuum.

The oily residue consisted of 36.0 g 2,4-dichlorophenoxyacetic acid methyl-( l-methylpropyl)-ketoxime ester (92% yield). n 1.5360. This ester will be referred to hereinafter as Compound No. l.

Compounds Nos. 2 to 122 were prepared in an analogous manner from starting materials which are commercially available to a large extent and are readily prepared by known methods as far as not available. These compounds and their melting points or indices of refraction are listed in attached Table I. They are colorless and odorless crystalline solids or oily liquids which are insoluble in water and benzene, but soluble in acetone, methylene chloride, tetrahydrofuran, dimethylformamide, cyclohexanone, and isophorone.

Examples 2 to 6 illustrate the use of compounds of the invention in combating weeds. The compounds were combined with the carriers mentioned in a conventional manner.

EXAMPLE 2 The compounds identified in Table 2 by the numbers assigned in Table 1 were applied at a rate of 3 kg of active agent per hectare in a greenhouse to cultures of four types of millet when the plants were at the two to three-leaf stage. The compounds were used in aqueous compositions in which the active agents were emulsified. and which were sprayed at a rate of 500 liters per hectare.

The plants were inspected 2 weeks after spraying, and the results achieved were evaluated on an empirical, numerical scale from 0 to 10, and value of 0 indicating total destruction, and a value of 10 the absence of damage recognizable from comparison with untreated controls of the same species.

EXAMPLE 3 The crop plants wheat, barley, rye, oats, and rice, and the common weeds identified in Table 3 were sprayed in a greenhouse after germination with aqueous emulsions of the compounds identified by the numbers assigned in Table l. The emulsions were applied at a rate of 500 liters per hectare corresponding to 1 kg active agent per hectare.

The plants were inspected 2 weeks after spraying and the effects of the compounds were evaluated on the scale described in Example 2. None of the crop plants were found to have suffered any effects while the weeds were totally destroyed or at least severely stunted in their growth, as is shown in the Table.

EXAMPLE 4 The weeds identified in Table 4 were sprayed after gennination with emulsions of the compounds of the invention identified by numbers assigned to them in Table 1 at a rate of 500 liters per hectare, corresponding to only 0.3 kg active agent per hectare. For comparison purposes, the weeds were also sprayed in the same manner with sodium 2,4-dichlorophenoxyacetate (Compound No. 123 Table 4 lists the results observed 2 weeks after spraying on the scale of Example 2.

EXAMPLE 5 The five crop plants mentioned in Example 3 and corn as well as six of the weeds mentioned in Example 3 were sprayed after germination with aqueous emulsions of compounds of the invention identified by numerals assigned to them in Table l at a rate of 0.3 kg active agent per hectare. For comparison purposes, 2- (2,4-dichlorophenoxy )-propionic acid (Compound N0. 124) was tested in the same manner.

None of the crop plants were damaged by any of the active agents tested. The effects on the weeds after 2 weeks are listed in Table 5 in the same manner as in the preceding Examples 2 to 4.

EXAMPLE 6 Setaria italica was sprayed in a greenhouse after germination with aqueous emulsions of compounds of the 6 Nos. 1 to 7, 9, 14 to 18, 22, 28, 34 to 39, 45, 48 to 50. 52, 54,55, 57 to 68, 70 to 73, 76, to 78, 80, 81, 100 to 111, and 114 to 122, while severe damage was produced by Compounds Nos. 8, 19, 23, 2932, 40, 43, 44,

invention at a rate of 500 liters per hectare, corre- 5 51, 53, 69, 79, 1 12, and 1 13. Only moderate damage spondmg to 5 kg active agent per hectare. Three was found in plants treated with Compounds Nos. 10 months after the spraying, the plants were inspected, and l 1, and experimental error may account for this and their condition was evaluated on a scale of to 4. fact. in which 0 indicates the absence of damage as com- The compounds enumerated in Table 1, but not menpared to an untreated plant, 1 indicates minor damage, tioned in Examples 2 to 6, were subjected to random 2 moderate damage, 3 severe damage, and 4 total despot tests whose results indicated that their herbicidal struction. effects are closely analogous to those of the compounds All tested compounds produced at least moderate, nearest in chemical composition which were tested long-term damage. More specifically, total destruction more extensively. was observed in the plants treated with Compounds TABLE 1 Compound n MP. "C

2 2-( ,4-Dichlorophenoxy)-propionic acid acetoxime ester 1.5390 3 2.4-Dichlurophenoxy-acetic acid acetoxime ester 81 4 2-Methyl-4-chlorophenoxy-acetic acid acetoxime ester 58 5 2,4-Dichlorophenoxy-acetic acid 3.5.5-trimethyl-2-cyc1ohexenonoxime ester 1 l2 6 2-Methy14-ch1orophenoxyacetic acid 3,5.5-trimethyI-Z-cyclohexenonoxime ester 96 7 2,4,5-Trichlorophenoxy-acetic acid acetoxime ester 83 8 2(2,4-Dichlorophenoxy)-propionic acid 3,5,5-trimethyl-2-cyc1ohe;tenonoxime ester 1.5495 9 2-(2-Methyl-4-ch1orophenoxy )-propionic acid acetoxirne ester 1.5248 10 2-(2,4Dich10r0pher|oxy)-pr0pi0nic acid acetophenonoxime ester 102 11 2-(2,4-Dich1orophenoxy)-propionic acid methylisobutylketoxime ester 1.5245 12 2-(2,4-Dichlorophenoxy]propionic acid 3-nitrobenzaldoxime ester 73 13 2-(2,4Dich1orophenoxy)-propionic acid benzophenonoxime ester 1.6005 14 2,4,S-Trichlorophenoxy-acetic acid cyclohexanonoxime ester 90 15 Z-Methyl-4 chlorophenoxy-acetic acid cyclohexanonoxime ester 1.5462 16 2-(2,4,S-Trich1oropheno ty)-propionic acid acetoxime ester 67 17 2-(2,4.S-Trichlorophenoxy)-propionic acid cyclohexanonoxirne ester 78 18 4-Bromophenoxy-acetic acid acetoxime ester 63 19 4-Bromophenoxy-acetic acid cyclohexanonoxirne ester 79 20 2-(2,4-Dimethy1phenoxyJ-propionic acid acetoxime ester 70 21 2,4-Dichlorophenoxy-acetic acid methylethylketoxirne ester 1.5461 22 2,4-Dichlorophenoxyacetic acid diethylketoxime ester 1.541 1 23 2,4-Dichlorophenoxy-acetic aid methylpropylketoxirne ester 56 24 2-(2.4-Dich1or0phenoxy)-propionic acid methy1ethy1ketoxime ester 1.5324 25 2-(2,4-Dich1orophenoxy)propionic acid diethylketoxime ester 1.5305 26 2-(2,4-Dichlorophenoxy)-propionic acid methylpropylketoxime ester 1.5292 27 3-Chlorophenoxy-acetic acid acetoxime ester 1.5406 28 2,4-Dichlorophenoxy-acetic acid methylisobutylketoxime ester 1.5354 29 2,4Dichlorophenoxy acetic acid methylisopropylketoxime ester 1.5383 30 2-Methyl-4-ch1orophenoxy-acetic acid methylethylketoxime ester 1.5330 31 2-Methyl-4-c1orophenoxy-acetic acid diethylketoxime ester 1.5297 32 2.-Methyl-4-chlorophenoxy-acetic acid methylpropylketoxime ester 60 33 2-(2, 4-Dich1orophenoxyHaropionic acid butyrophenonoxirne ester 1.5666 34 2-Methy1-4 ch1orophenoxy-acetic acid diisobutylketoxime ester 1.51 12 35 2'(2,4-Dich1orophenoxy)-propionic acid diisobutylketoxime ester 1.5140 36 2 (2Methy1-4ch1orophenoxytpropionip acid diisobutylketoxime ester 1.5040 37 2,4-Dichlorophenoxy-acetic acid diisobutylketoxime ester 1.5210 38 2,4-Dichlorophenoxy-acetic acid phenoxyacetoxime ester 1.5720 39 2-(2,4-Dichlorophenoxy)-propionic acid phenoxyacetoxime ester 1.5628 40 2-(2-Methy1-4ch1orophenoxyJ-propionic acid diethylketoxime ester 1.5179 41 2-(2-Methyl-4-chlorophenoxy )-propionic acid methylethylketoxime ester 1.5223 42 2-(2-Methy1-4-ch1orophenoxy)-propionic acid methylpropylketoxime ester 1.5177 43 2-[2-Methy14-ch1orophenoxy )-propionic acid methylisobutylketoxime ester 1.5125 44 2,4.S-Trichlorophenoxy-acetic acid diethylketoxime ester 55 45 2,4,5-Trichlorophenoxy-acetic acid methylethylketoxime ester 1.5581 46 2,4,5-Trich1orophen0xy-acetic acid methylpropylketoxime ester 1.5450 47 2,4,5Trichlorophenoxy-acetic acid methylisobutylketoxime ester 1.5261 48 2-Methyl-4-chlorophenoxy-acetic acid dipropylketoxime ester 1.5210 49 2,4-Dichlorophenoxy-acetic acid dipropylketoxime ester 1.5319 50 2-( ,4-Dich1orophenoxy)-propionic acid dipropylketoxime ester 1.5210 51 2.4,5Trichlorophenoxy-acetic acid dipropylketoxirne ester 44 52 2.4,5-Trichlorophenoxy-acetic acid diisobutylketoxime ester 1.5287 53 2-(2-Methy1-4-ch1orophenoxyJ-propionic acid dipropylketoxime ester 1.5090 54 2-Methy1-4-ch1or0phenoxyacetic acid methylisopropylketoxime ester 1.5282 55 2-( 2Methy1-4-chlor0phenoxy)-propionic acid methylisopropylketoxime ester 1.5163 56 2-(2.4-Dichlorophenoxy) propionic acid methylisopropylketoxime ester 1.5283 57 2,4.5-Trichlorophenoxy-acetic acid methylisopropylketoxirne ester 72 58 2-Methyl-4-ch1orophenoxy-acetic acid methylhexyiketoxime ester 1.5160 59 2,4 Dichlorophenoxy-acetic acid methylhexylketoxime ester 1.5255 60 2-(Z-MethylA-chlorophenoxy)propionic acid methylhexylketoxime ester 1.5080 61 2-(2,4-Dichlorophenoxy)-propionic acid methylhexylketoxime ester 1.5182 62 2,4.5-Trich1orophenoxy-acetic acid methylhexylketoxime ester 1.5328 63 2-( 2-Methy1 4-ch1orophenoxy)-propionic acid 3.5.5-trimethyl-Lcyclohexenonoxime ester 1.5418 64 2,4-Dichlorophenoxyacetic acid 3,5-dirnethy1-2-cyc10hexerionoxime ester 80 65 2-(2,4-Dichlorophenoxy)-propionic acid 3,S-dimethyI-Z-cyclohexenonoxime ester 1.5571 66 2,4,5-Trichlorophen0xy-acetic acid 3,5,5-trimethyl-Z-cyclohexenonoxime ester 1.5678 67 2,4-Dichlorophenoxy-acetic acid cyclohexanonoxime ester 1.5569 68 242,4-Dich1orophenoxyJ-propionic acid cyclohcxanonoxime ester 1.5489 69 2-(2'Methy14-ch1orophenoxy)propionic acid cyclohexanonoxime ester 1.5372 70 2,4-Dichlorophenoxy-acetic acid methyl-2-methoxyethy1ketoxime ester 1.5412 71 2-(2,4-Dichlorophenoxy)-propionic acid methyl-Z-methoxyethyiketoxime ester 1.5311 72 2Methyl-4-chlorophenoxy-acetic acid ethylbutylketoxime ester 1.5200

TABLE 1 -continued N11 Compound n MP, C 73 2,4-Dich1nrophenoxy-acetic acid ethylbutylketoxime ester 1.5292 74 2-(IMethyL-i-chlorophenoxyi-propionic acid ethylhutylketoxime ester 1.5122 75 2-(2,4Dich1urophenoxy)-propionic acid ethylbutylketoxime ester 1.5218 76 2,4,5-Trich1orophen0xyacetic acid ethylbutylketoxime ester 1.5375 77 2-Methyl-4-ch10rophenoxy-acetic acid cyclopentanonoxirne ester 72 78 2.4 Dichlorophenoxy-acetic acid cyclopentanonoxime ester oil 79 2 4.5-Trichlorophenoxy-acetic acid cyclopentanunoxime ester 100-102 80 2 Methyl-4-ch1orophenoxy-acetic acid 3-methy1-cyc1opentanonoxime ester 71-72 81 2,4-Dich1orophenoxyacetic acid 3-methy1-cyclopentanon0xime ester 1.5485 82 2,4-Dichlorophenoxyacetic acid ethylpentylketoxime ester 1.5269 83 2-14-Ch10ro-2-methy1phcnoxy1-pr0pionic acid ethylpentylketoxime ester 1.5072 84 2 (2 4-Dich1orophenoxy )-propionic acid cthylpentylketoxime ester 1.5 2 85 2,4.5-Trich1orophenoxy-acetic acid ethyipentylketoxime ester .5321 86 4-Ch10r0-2methy1phcn0xy-acetic acid ethylpentylketoxime ester 1.5158 87 2.4-Dichlorophenoxy-acetic acid ethy1isopropy1ketoxime ester 1.5338 88 2.4.S-Trichlornphenoxy-acetic acid ethylisopropylkctoxime ester 1.5400 89 24 2-Methy1 4-c1i1orophenoxypropinnic acid ethy1isopropy1ketoxime ester 1.5142 2-( 2.4-Dichlr0phenoxy )-propionic acid ethyiisopropylketoxime ester 1.5240 90 91 2 Methy14-ch10rophen0xy-acetic acid ethylisopropylketoxime ester 1.5237 92 4Ch10r0-2-methy1phenoxy-acetic acid isopropylpentylketoxime ester 1.5109 93 2.4-Dich10ruphenoxy-acetic acid isopropyipentyiketoxime ester 1.5204 94 2 (4-Chitiro-Z-methylphenoxy)-propionic acid isopropylpentylketuxime ester 1.5031 95 4-Chloro-Z-methylphenoxy-acetic acid ethyipropylketoxime ester 1.5229 96 2.4-Dichioruphenoxy-acetic acid methyi-tert-butylketoxime ester 56 97 2(4-Ch1oro2-methylphenoxy)-propionic acid methyl-tert.buty1ketoxime ester 1.5156 98 2(2 4-Dich1orophen0xy )-propionic acid isopropylpentylketoxime ester 1.5128 99 2,4-Dich1orophenoxy-acetic acid isopentylmethylketnxime ester 1.5302 100 2l4'Chlor0-2-methy1-phen0xyl-propi0nic acid isopentylmethylketnxime ester 1.5075 101 4-Chl0r02-methy1phenoxyacetic acid isopenty1methy1ketoxime ester 1.5187 102 2,4.5-Trich1orophenoxy-acetic acid isopenty1methy1ketoxime ester 1.5354 103 2-(4-Ch1oroQ-methylphenoxy)-pr0pionic acid butylmethylketoxime ester 1.5119 104 2,4-Dichlorophenoxy-acetic acid butylmethylketoxime ester 1.5338 I 2(2,4-Dichlorophenoxy1-propionic acid isopentylmethylketoxime ester 1.5215 106 242.4-Dichrophenoxy] prupionic acid butylmethyiketoxime ester 1.5246 10" 2,4.5Trich10rophenoxya|:etic acid butylmethylketuxime ester 1.5351 108 l4-Chloru-2methylphenoxy)-acetic acid butylmethylketoxime ester 1.5208 109 2,4,5-Trichlorophenoxy-acetic acid methy1-tert.-buty1ketoxime ester 106 1 10 2-(2,4-Dichlorophenoxy)-propi0nic acid methybtert.-1Juty1ketoxime ester 1.5246 1 l 1 4-Ch1or0-2-methy1phenoxy-acelic acid methyl-tert.-buty1ketoxime ester 1.5209 1 12 2-(2Methy14-ch1orophenoxy)-propionic acid 3-methy1 cyclopentanonoxime ester 1.5272 1 13 2-(2.4-Dich1orophenoxy )-propi0nic acid 3-methylcyciopentanonoxime ester 1.5418 1 14 2.4-Dichlorophenoxy-acetic acid ethylpropylketoxime ester 1.5282 1 2-(2 4-Dich1orophenoxyJ-propionic acid ethyipropylketoxime ester 1.5240 1 16 2-(2-Methy1-4-ch1orophcnoxy)-propionic acid ethylpropylketoxime ester 1.5133 1 17 2,4 5-Trich1orophenoxy-acetic acid ethylpropylketoxime ester 1.5440 1 18 2.4.5-Trich1orophenoxy-acetic acid 3'methyi-cyclopentanonoxime ester 1 19-120 1 19 2-Methyl4-chlorophenoxy-acetic acid diisopropyloxime ester 1.5173 120 2.4-Dichlorophenoxy-acetic acid diisopropyioxime ester 1.5271 121 2-(2Methy1-4-ch1orophenoxy)-propionic acid diisopropyloxime ester 1.5092 122 2-12.4-Dichk1r0phenoxy)propi0nic acid diisopropyioxime ester 1.5190

TABLE 2 Compound No. 2 3 4 9 16 17 21 23 2B 29 3O 31 32 34 36 37 38 43 44 46 47 48 49 Digitaria 214-35--2334-5 sanguinafis Echinochioa 1225455315542125444345300 crus galli Setariaitaiica 1 0 1 1 2 3 5 5 1 4 5 5 5 2 l 1 5 4 4 4 4 1 0 0 0 Setaria faberii 1 0 0 1 3 3 3 4 1 3 2 5 5 2 3 1 4 4 4 5 0 1 1 TABLE 3 Compound No. 2 3 4 5 6 8 9 1O 12 13 14 15 22 24 25 26 33 39 41 42 51 Slcllaria media 11 0 1 4 3 O 0 1 1 1 4 4 4 1 3 l 2 U 0 O 0 2 Scnecio vulgaris 0 1 0 l I 4 4 2 2 2 1 2 4 3 2 2 1 1 0 1 Matricaria 4 4 5 re w 3 a M 5 chamumilla Lamium 43-4-2 -52--1(I amplexicaule Centaurea cyanus 0 0 0 2 1 3 4 i 2 l 2 l 3 3 3 2 3 2 3 0 3 Amaranthus O 0 0 1 l1 0 0 1 U 2 4 1 1 5 2 1 2 1 2 l rctroflcxus Galium uparinc 0 3 2 1] 1 4 1 0 1 Chrysanthemum 3 1 l l 3 5 3 3 7 2 3 2 4 5 4 4 3 3 segetum lpomea purpurea l1 0 0 l 0 2 5 l 3 3 O (1 0 4 l 4 2 2 1 0 Pnlygonum U 0 1 1 l 0 l 1 1 1 1 0 [1 1 4 2 2 2 0 3 lapathifuiium TABLE 4 Compound No. 3 22 49 123 Stellaria media 5 6 2 7 Senecio vulgaris 2 3 l S Matricaria chamomilla 5 l0 I0 10 Lamium amplexicaule l0 l0 6 l0 Centaurea cyanus 3 8 0 4 Amaranthus retroflexus 3 2 5 8 Galium aparine l0 l0 4 l0 Chrysanthemum segetum 3 4 4 8 lpomea purpurea 0 0 0 l Polygonum lapathifolium 0 0 0 8 TABLE 5 Compound No. 11 26 35 so 56 61 68 72 73 74 1 4 Stellaria media 2 4 4 4 3 3 4 3 6 Senecio vulgaris 2 2 l 3 l 2 5 2 l l [0 Lamium amplexicaule 2 2 4 l 2 3 5 3 2 l0 Centaurea cyanus 4 6 6 2 0 4 2 2 6 l0 Galium aparine 3 l 2 3 I 2 l 5 lpomea purpurea 2 l 5 1 3 3 3 3 4 'I What is claimed is: 1. A compound of the formula methoxymethyl, phenyl, nitrophenyl, methylphenyl,

chlorophenyl, and hydrogen except that R, and R cannot both be hydrogen; R and R taken together with R the adjacent carbon atom can be cyclopentylidene, 3- o l methylcyclopentylidene, cyclohexlidene, dimethylcyy 0- e c O N R clohexylidene or trimethylcyclohexylidene; R, can be R 1 hydrogen or methyl and X, Y, and Z taken individually Z 3 can be hydrogen, methyl or a halogen.

wherein R and R each represent a member selected from one to six carbon atoms, phenoxyrnethyl, 2-

2. A compound as set forth in claim 1, wherein at least one of said X, Y, and Z is halogen.

3. A compound as set forth in claim 2, wherein said lower alkyl is methyl, and said alkoxy is methoxy. 

1. A COMPOUND OF THE FORMULA
 2. A compound as set forth in claim 1, wherein at least one of said X, Y, and Z is halogen.
 3. A compound as set forth in claim 2, wherein said lower alkyl is methyl, and said alkoxy is methoxy. 